CN119162679B - A method for preparing bamboo charcoal/regenerated cellulose composite fiber - Google Patents
A method for preparing bamboo charcoal/regenerated cellulose composite fiber Download PDFInfo
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- CN119162679B CN119162679B CN202411366518.7A CN202411366518A CN119162679B CN 119162679 B CN119162679 B CN 119162679B CN 202411366518 A CN202411366518 A CN 202411366518A CN 119162679 B CN119162679 B CN 119162679B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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Abstract
本发明公开了一种竹炭/再生纤维素复合纤维的制备方法，包括以下步骤：S1、获得竹炭颗粒；S2、将竹炭分散，加入多巴胺、三羟甲基氨基甲烷和功能性纳米粒子，得到聚多巴胺改性竹炭分散液；S3、加入聚硅氧烷季铵盐，得到改性竹炭；S4、将改性竹炭、纤维素和有机溶剂混合，得到改性竹炭再生纤维素纤维纺丝液；S5、经湿法纺丝，得到改性竹炭/再生纤维素复合纤维。本发明采用了聚多巴胺提高竹炭颗粒表面活性基团的密度，同时利用其修饰效果与纳米粒子的牢固结合，增加活性位点数量，提高竹炭与聚硅氧烷季铵盐的接枝效率，实现竹炭与基体的相互作用以及在基体中的分散性，从而所制备改性竹炭/再生纤维素复合纤维具有优异的抗菌性能和力学性能。
The invention discloses a method for preparing bamboo charcoal/regenerated cellulose composite fiber, comprising the following steps: S1, obtaining bamboo charcoal particles; S2, dispersing bamboo charcoal, adding dopamine, tris(hydroxymethyl)aminomethane and functional nanoparticles to obtain polydopamine modified bamboo charcoal dispersion; S3, adding polysiloxane quaternary ammonium salt to obtain modified bamboo charcoal; S4, mixing modified bamboo charcoal, cellulose and organic solvent to obtain modified bamboo charcoal regenerated cellulose fiber spinning solution; S5, wet spinning to obtain modified bamboo charcoal/regenerated cellulose composite fiber. The invention adopts polydopamine to increase the density of active groups on the surface of bamboo charcoal particles, and at the same time utilizes its modification effect to firmly combine with nanoparticles to increase the number of active sites, improve the grafting efficiency of bamboo charcoal and polysiloxane quaternary ammonium salt, realize the interaction between bamboo charcoal and matrix and the dispersibility in the matrix, so that the prepared modified bamboo charcoal/regenerated cellulose composite fiber has excellent antibacterial properties and mechanical properties.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a preparation method of bamboo charcoal/regenerated cellulose composite fibers.
Background
The bamboo charcoal fiber is a novel functional fiber developed by combining bamboo charcoal with textile fiber, and has the characteristics of adsorption performance, bacteriostasis, antibiosis, far infrared ray, negative ion, heat accumulation, warmth retention, moisture absorption, ventilation, environment friendliness and the like. At present, the bamboo charcoal fiber has important application prospects in the fields of clothing, home textiles, medical protective clothing, military and aerospace operator protective clothing, household electrical appliance electromagnetic radiation protection masks, air filtering materials and the like.
The regenerated cellulose fiber is prepared by taking natural polymer cellulose (wood pulp, cotton linter and the like) as a raw material and adopting a chemical method, wherein the chemical composition of the natural polymer cellulose is basically the same as that of the original polymer, and the cellulose structure is II type regenerated chemical fiber. However, when the size of the bamboo charcoal particles is too large or the addition amount of the bamboo charcoal particles in the cellulose solution is high, the bamboo charcoal is agglomerated in the slurry and cannot be stably dispersed, so that the spinnability of the bamboo charcoal fiber and the distribution uniformity of the bamboo charcoal in the fiber are affected, and the mechanical property and the functionality of the bamboo charcoal fiber are further affected. Therefore, the addition amount of the bamboo charcoal in the market is generally below 3%, and the addition amount of the bamboo charcoal is low, so that the obtained bamboo charcoal fiber has poor functions of adsorption, antibiosis, bacteriostasis and the like. Therefore, how to solve the problem of uniform and stable dispersion of the bamboo charcoal in the polymer matrix and to improve the interface interaction between the polymer and the bamboo charcoal under the condition of high addition amount of the bamboo charcoal, and how to obtain the high-performance multifunctional bamboo charcoal fiber becomes difficult and key.
The Chinese patent publication No. CN110158175B discloses a bamboo charcoal slurry for spinning viscose stock solution and a preparation method thereof, and the method uses a protein type surfactant and a rosin-based hyperbranched surfactant with a specific structure as a dispersing agent together, and utilizes the compounding of the two surfactants to play a synergistic effect, thereby being beneficial to the stable dispersion of the bamboo charcoal powder in an aqueous system. The Chinese patent publication No. CN100558952C discloses a bamboo charcoal viscose fiber and a manufacturing method thereof, wherein the surfactant is dialkyl dimethyl ammonium chloride or polyalkyl trimethyl ammonium chloride, and the dispersing agent is polysiloxane quaternary ammonium salt, dialkoxy silane quaternary ammonium salt or sodium tripolyphosphate. However, the existing method for improving the dispersion stability and particle size distribution of bamboo charcoal slurry by adding a surfactant still cannot meet the continuous spinning requirement of viscose liquid, is easy to generate agglomeration and deposition in the spinning process, brings the problems of poor spinnability, easy broken spinning ends and the like in the spinning process, and has uneven distribution and multiple flaws in viscose fibers.
The organic functionalization modification of the surface of the bamboo charcoal is another effective way to improve the dispersibility of the bamboo charcoal in the organic matrix, and can also give more excellent properties to the bamboo charcoal. Patent CN115318260A provides a co-modification of manganese and cyclodextrin, which can improve the dispersibility of the material, increase the active sites of the material and greatly improve the adsorption and degradation properties, but the excessive granularity of the bamboo charcoal can not meet the granularity requirement of fiber spinning.
Therefore, the development of an efficient and environment-friendly modification method for preparing the functional bamboo charcoal, and the high-density modification of the functional bamboo charcoal material in the regenerated cellulose matrix and the interfacial effect are significant.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a preparation method of bamboo charcoal/regenerated cellulose composite fiber.
In order to achieve the aim, the technical scheme adopted by the invention is that the preparation method of the bamboo charcoal/regenerated cellulose composite fiber comprises the following steps:
S1, crushing and sieving bamboo charcoal, washing with water and drying to obtain bamboo charcoal particles;
S2, dispersing bamboo charcoal in water, adding dopamine and tris (hydroxymethyl) aminomethane, adjusting the pH value, and adding functional nano particles during stirring to obtain polydopamine modified bamboo charcoal dispersion liquid;
s3, adding polysiloxane quaternary ammonium salt into the polydopamine modified bamboo charcoal dispersion liquid, carrying out surface in-situ polymerization, and centrifugally washing and drying to obtain modified bamboo charcoal;
S4, mixing the modified bamboo charcoal, cellulose and an organic solvent to obtain a modified bamboo charcoal regenerated cellulose fiber spinning solution;
s5, carrying out wet spinning on the modified bamboo charcoal regenerated cellulose fiber spinning solution, and drying to obtain the modified bamboo charcoal/regenerated cellulose composite fiber.
In a preferred embodiment of the present invention, in the step S1, the preparation of the bamboo charcoal includes the following steps:
S11, cleaning the bamboo, and drying at 50-80 ℃ for 3-6 hours;
s12, treating the dried bamboo in an oxygen-free atmosphere at the temperature of 230-300 ℃ for 1-2 hours, heating to 450-600 ℃, treating for 2-4 hours, and gradually cooling carbonized bamboo charcoal from the highest calcination temperature to 50-60 ℃ to obtain a bamboo charcoal blank;
And S13, cleaning the bamboo charcoal blank to be neutral, and drying at the temperature of 60-100 ℃ for 1-3 hours to obtain the bamboo charcoal with the carbon-nitrogen ratio of 86.25-135.42.
In a preferred embodiment of the present invention, in the step S1, the bamboo charcoal crushing includes mechanical ball milling and air flow milling, the milling time is 2-8 hours, and the particle size of the crushed bamboo charcoal is 1-20 μm.
In a preferred embodiment of the present invention, in the step S2, the functional nanoparticle is one of a silver nanoparticle and a zinc oxide nanoparticle, the particle size is 24-100 nm, the mass ratio of the bamboo charcoal, the dopamine, the tris (hydroxymethyl) aminomethane, the functional nanoparticle and the water is 1-3:0.25-2.4:0.25-3.5:0.5-1.5:100, the pH is 7-9, and the stirring modification time is 2-6 h.
In a preferred embodiment of the present invention, in the step S3, the quaternary polysiloxane salt is one of 3- (trimethoxysilyl) propyl hexadecyl dimethyl ammonium chloride, 3- (trimethoxysilyl) propyl octadecyl dimethyl ammonium chloride, 3- (triethoxysilyl) propyl hexadecyl dimethyl ammonium chloride, or 3- (triethoxysilyl) propyl octadecyl dimethyl ammonium chloride.
In a preferred embodiment of the present invention, in the step S3, the mass ratio of the polysiloxane quaternary ammonium salt to the bamboo charcoal is 15-30:1, and the in-situ polymerization time of the surface is 4-8 hours.
In a preferred embodiment of the present invention, in the step S4, the mass ratio of the modified bamboo charcoal, the cellulose and the organic solvent is 0.1-0.3:3-8:85.
In a preferred embodiment of the present invention, in the step S4, the cellulose is one of bamboo pulp, cotton pulp, wood pulp or hemp pulp, and the organic solvent is one of sodium sulfonate solution, tetrabutylammonium hydroxide/urea solution, alkali/urea solution, N-methylmorpholine-N-oxide solution or 1-allyl-3-methylimidazole chloride ionic liquid.
In a preferred embodiment of the present invention, in the step S5, the modified bamboo charcoal regenerated cellulose fiber spinning solution is centrifuged to remove air bubbles before the wet spinning.
In a preferred embodiment of the present invention, in the step S5, the modified bamboo charcoal/regenerated cellulose composite fiber is drawn for 2 times, and the drawing multiple is 0.9-1.4.
The invention solves the defects existing in the background technology, and has the following beneficial effects:
(1) The invention provides a preparation method of bamboo charcoal/regenerated cellulose composite fiber, which adopts high-density modification of polydopamine on the surface of a bamboo charcoal material to obviously improve the density of active groups on the surface of bamboo charcoal particles, is favorable for improving the grafting efficiency of polysiloxane quaternary ammonium salt after secondary modification, and simultaneously utilizes the modification effect of polydopamine to firmly combine with nano particles to increase the number of active sites on the surface of the bamboo charcoal, so that the grafting efficiency of the bamboo charcoal and the polysiloxane quaternary ammonium salt is further improved, the interaction of functional bamboo charcoal filler and a matrix and the dispersibility in the matrix are realized, and the prepared modified bamboo charcoal/regenerated cellulose composite fiber has excellent antibacterial property and mechanical property.
(2) According to the invention, the polysiloxane quaternary ammonium salt modified bamboo charcoal is obtained in an in-situ polymerization mode, the method is simple and convenient to operate, the method is environment-friendly, the hydrophilicity and the antibacterial property of the bamboo charcoal are enhanced, the long-chain structure of the polysiloxane quaternary ammonium salt is also beneficial to improving the dispersibility of the bamboo charcoal in a regenerated cellulose matrix, and further, the mechanical properties of fibers are also influenced to a certain extent, because the polysiloxane quaternary ammonium salt molecules contain quaternary ammonium groups, due to the fact that the dopamine forms a polydopamine layer on the surface of the bamboo charcoal, the polysiloxane quaternary ammonium salt has good adhesiveness and reactivity, and further, when the polysiloxane quaternary ammonium salt is grafted to the surface of the bamboo charcoal through chemical bonds, the quaternary ammonium groups are firmly fixed on the bamboo charcoal particles, and the antibacterial property of the fibers is effectively improved along with the dispersion of the bamboo charcoal particles in the regenerated cellulose fibers, and meanwhile, the functional groups in the polysiloxane quaternary ammonium salt molecules can form hydrogen bonds or ionic bonds with hydroxyl groups in the surface of the bamboo charcoal and the regenerated cellulose fibers, so that the compatibility between the bamboo charcoal and the regenerated cellulose fibers is enhanced, and the mechanical interface is also improved, and the performance of the fibers is better improved.
(3) In the invention, the functional nano particles endow the composite fiber with additional antibacterial and mechanical properties, because the positive charges on the surfaces of the functional nano particles and the negative charges on the cell walls of bacteria generate differences, the nano particles can be strongly adsorbed on the surfaces of the bacteria and damage the integrity of cell membranes of the bacteria through electrostatic interaction, meanwhile, the active sites on the surfaces of the nano particles can react with biomolecules in the bacteria to further inhibit or kill the bacteria, and the functional nano particles have larger specific surface area and rich surface chemical properties, so that the nano particles can form strong interaction with the active sites on the surfaces of the bamboo charcoal, the number of the active sites on the surfaces of the bamboo charcoal is increased, more grafting positions are provided for the quaternary ammonium salt of polysiloxane, and therefore, the grafting efficiency is improved, and the antibacterial and mechanical properties are further improved.
(4) In the invention, the high carbon-nitrogen ratio bamboo charcoal has more micropores, specific surface area and unsaturated bonds, is beneficial to more uniform deposition of polydopamine on the surface of the bamboo charcoal, increases the available space of surface active groups, has more carbon-based active sites on the surface of the high carbon-nitrogen ratio bamboo charcoal, can be used as a catalytic center of polydopamine polymerization reaction, enables carbon atoms in the bamboo charcoal to form stronger chemical bonds with nitrogen atoms in polydopamine, and can enable interaction between the bamboo charcoal and polydopamine to be stronger, thereby enhancing the interfacial binding force between the bamboo charcoal and polydopamine, and further being beneficial to improving grafting effect and further improving antibacterial performance and mechanical property of the polydopamine.
(5) In the invention, by providing an alkaline modification environment, functional groups such as amino groups, catechol groups and the like in dopamine molecules are more easily deprotonated to form negatively charged ions, electrostatic interaction and hydrogen bonding can be generated, and the self-polymerization capability of dopamine is promoted, so that the dopamine can be applied to surface modification of functional nanoparticles, the charge stabilization of the surfaces of the nanoparticles is facilitated, the stability and the dispersibility of the nanoparticles in aqueous solution can be remarkably improved, and agglomeration is prevented, thereby realizing the synergistic effect of dopamine, the functional nanoparticles and polysiloxane quaternary ammonium salt and effectively improving the antibacterial effect and the mechanical property.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art;
FIG. 1 is a microscopic topography of the surface of the bamboo charcoal fiber prepared in example 1 (a) and example 2 (b) of the present invention;
FIG. 2 is a cross-sectional micro-morphology graph of the bamboo charcoal fiber prepared in examples 1 (a) and (b) and examples 2 (c) and (d) of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
The raw materials, equipment, reagents and the like used in the invention can be purchased in the market or prepared by the prior art.
The preparation method of the bamboo charcoal/regenerated cellulose composite fiber comprises the following steps:
S1, crushing and sieving bamboo charcoal, washing with water and drying to obtain bamboo charcoal particles;
S2, dispersing bamboo charcoal in water, adding dopamine and tris (hydroxymethyl) aminomethane, adjusting the pH value, and adding functional nano particles during stirring to obtain polydopamine modified bamboo charcoal dispersion liquid;
s3, adding polysiloxane quaternary ammonium salt into the polydopamine modified bamboo charcoal dispersion liquid, carrying out surface in-situ polymerization, and centrifugally washing and drying to obtain modified bamboo charcoal;
S4, mixing the modified bamboo charcoal, cellulose and an organic solvent to obtain a modified bamboo charcoal regenerated cellulose fiber spinning solution;
s5, carrying out wet spinning on the modified bamboo charcoal regenerated cellulose fiber spinning solution, and drying to obtain the modified bamboo charcoal/regenerated cellulose composite fiber.
The dispersing method commonly used in the field is applicable to the invention, and in one embodiment of the invention, the dispersing method is that after bamboo charcoal and a solution are magnetically stirred and mixed, the ultrasonic wave is carried out for 10-60 min at normal temperature.
In some embodiments, in step S1, the preparation of the bamboo charcoal comprises the steps of:
S11, cleaning the bamboo, and drying at 50-80 ℃ for 3-6 hours;
s12, treating the dried bamboo in an oxygen-free atmosphere at the temperature of 230-300 ℃ for 1-2 hours, heating to 450-600 ℃, treating for 2-4 hours, and gradually cooling carbonized bamboo charcoal from the highest calcination temperature to 50-60 ℃ to obtain a bamboo charcoal blank;
And S13, cleaning the bamboo charcoal blank to be neutral, and drying at the temperature of 60-100 ℃ for 1-3 hours to obtain the bamboo charcoal with the carbon-nitrogen ratio of 86.25-135.42.
In the step S11, bamboo in eastern region of hunan was used as a raw material.
In some specific embodiments, in the step S1, the bamboo charcoal crushing comprises mechanical ball milling and air flow milling, wherein the grinding time is 2-8 hours, and the particle size of the crushed bamboo charcoal is 1-20 mu m.
In some specific embodiments, in the step S2, the functional nano particles are silver nano particles or zinc oxide nano particles, the particle size is 24-100 nm, the mass ratio of the bamboo charcoal to the dopamine to the tris (hydroxymethyl) aminomethane to the functional nano particles to the water is 1-3:0.25-2.4:0.25-3.5:0.5-1.5:100, the pH value is 7-9, and the stirring modification time is 2-6 h.
In some specific embodiments, in the step S3, the polysiloxane quaternary ammonium salt is one of 3- (trimethoxysilyl) propyl hexadecyl dimethyl ammonium chloride, 3- (trimethoxysilyl) propyl octadecyl dimethyl ammonium chloride, 3- (triethoxysilyl) propyl hexadecyl dimethyl ammonium chloride or 3- (triethoxysilyl) propyl octadecyl dimethyl ammonium chloride, the mass ratio of the polysiloxane quaternary ammonium salt to the bamboo charcoal is 15-30:1, and the surface in-situ polymerization time is 4-8 hours.
In some specific embodiments, in the step S4, the mass ratio of the modified bamboo charcoal to the cellulose to the organic solvent is 0.1-0.3:3-8:85, the cellulose is one of bamboo pulp, cotton pulp, wood pulp or hemp pulp, and the organic solvent is one of sodium sulfonate solution, tetrabutylammonium hydroxide/urea solution, alkali/urea solution, N-methylmorpholine-N-oxide solution or 1-allyl-3-methylimidazole chloride ionic liquid.
In some specific embodiments, in the step S5, before wet spinning, the modified bamboo charcoal regenerated cellulose fiber spinning solution is centrifuged to remove bubbles, and the modified bamboo charcoal/regenerated cellulose composite fiber is subjected to 2-pass drafting, wherein the drafting multiple is 0.9-1.4.
Example 1
The preparation method of the bamboo charcoal/regenerated cellulose composite fiber comprises the following steps:
S1, cleaning bamboo, and drying at 60 ℃ for 4 hours;
S2, treating the dried bamboo in a nitrogen atmosphere at the temperature of 260 ℃ for 1.5 hours, heating to 520 ℃, treating for 2 hours to finish carbonization, and gradually cooling carbonized bamboo charcoal from the temperature of 520 ℃ to 50 ℃ to obtain a bamboo charcoal blank;
S3, cleaning the bamboo charcoal blank to be neutral, and drying at the temperature of 80 ℃ for 2 hours to obtain bamboo charcoal with the carbon-nitrogen ratio of 92.18;
s4, putting bamboo charcoal with the carbon-nitrogen ratio of 92.18 into a high-energy ball mill for ball milling for 5 hours, grinding, passing the ground bamboo charcoal into a particle size of 2 mu m, mixing 10g of refined bamboo charcoal powder with 1000ml of water, centrifugally washing at the speed of 4000r/min for 2 times, and drying the cleaned bamboo charcoal in a drying oven to obtain bamboo charcoal particles;
S5, dispersing 2g of bamboo charcoal in 100ml of water, stirring for 5min, oscillating for 10min by adopting ultrasonic waves, adding 1g of dopamine for magnetic stirring, adding 1.3g of tris buffer solution, adjusting the pH value of the mixed solution to 8.5, stirring for 4h, and adding 0.5g of silver nano particles with the particle size of 24nm during stirring to obtain polydopamine modified bamboo charcoal dispersion;
S6, adding 25ml of 3- (trimethoxysilyl) propyl hexadecyl dimethyl ammonium chloride into the polydopamine modified bamboo charcoal dispersion liquid, stirring for 5 hours, centrifugally cleaning at the speed of 4000r/min, washing with water to remove organic monomers, and vacuum drying at the temperature of 60 ℃ to obtain modified bamboo charcoal;
S7, adding 1.1g of modified bamboo charcoal into 220g of urea/tetrabutylammonium hydroxide mixed solvent (the mass ratio is 2:5, and the tetrabutylammonium hydroxide solution is 40% aqueous solution), stirring to uniformly disperse the solvent, adding 12.5g of crushed bamboo pulp into the mixed solvent, and stirring to dissolve to obtain the modified bamboo charcoal regenerated cellulose fiber spinning solution;
S8, centrifuging the modified bamboo charcoal regenerated cellulose fiber spinning solution to remove bubbles, carrying out wet spinning, and sequentially passing through a coagulating bath, a first drafting roller, a water bath, a second drafting roller and a drying box to obtain the modified bamboo charcoal/regenerated cellulose composite fiber, wherein the coagulating bath is a mixed solution of citric acid, sodium citrate, ethylene glycol and water, the mass ratio is 14:5:80:110, the coagulating bath temperature is 25 ℃, the cleaning tank solution is water, the first drafting multiple is 1.1, the second drafting multiple is 1.0, and the drying temperature is 80 ℃.
Example 2
The preparation method of the bamboo charcoal/regenerated cellulose composite fiber comprises the following steps:
S1, cleaning bamboo, and drying at 60 ℃ for 4 hours;
S2, treating the dried bamboo in a nitrogen atmosphere at the temperature of 260 ℃ for 1.5 hours, heating to 520 ℃, treating for 2 hours to finish carbonization, and gradually cooling carbonized bamboo charcoal from the temperature of 520 ℃ to 50 ℃ to obtain a bamboo charcoal blank;
S3, cleaning the bamboo charcoal blank to be neutral, and drying at the temperature of 80 ℃ for 2 hours to obtain bamboo charcoal with the carbon-nitrogen ratio of 92.18;
s4, putting bamboo charcoal with the carbon-nitrogen ratio of 92.18 into a high-energy ball mill for ball milling for 5 hours, grinding, passing the ground bamboo charcoal into a particle size of 2 mu m, mixing 10g of refined bamboo charcoal powder with 1000ml of water, centrifugally washing at the speed of 4000r/min for 2 times, and drying the cleaned bamboo charcoal in a drying oven to obtain bamboo charcoal particles;
S5, dispersing 2g of bamboo charcoal in 100ml of water, stirring for 5min, oscillating for 10min by adopting ultrasonic waves, adding 1g of dopamine for magnetic stirring, adding 1.3g of tris buffer solution, adjusting the pH value of the mixed solution to 8.5, stirring for 4h, and adding 0.5g of zinc oxide nano particles with the particle size of 24nm during stirring to obtain polydopamine modified bamboo charcoal dispersion;
S6, adding 25ml of 3- (trimethoxysilyl) propyl hexadecyl dimethyl ammonium chloride into the polydopamine modified bamboo charcoal dispersion liquid, stirring for 5 hours, centrifugally cleaning at the speed of 4000r/min, washing with water to remove organic monomers, and vacuum drying at the temperature of 60 ℃ to obtain modified bamboo charcoal;
S7, adding 1.1g of modified bamboo charcoal into 240g of mixed solvent of NaOH/urea/water (the mass ratio is 7:12:81), stirring to uniformly disperse the solvent, adding 12g of crushed bamboo pulp into the mixed solvent, and stirring to dissolve to obtain a modified bamboo charcoal regenerated cellulose fiber spinning solution;
S8, carrying out vacuum degassing on the modified bamboo charcoal regenerated cellulose fiber spinning solution, and then carrying out dry-wet spinning, wherein the modified bamboo charcoal/regenerated cellulose fiber spinning solution sequentially passes through an air layer, a coagulating bath, a first drawing roller, a water bath, a second drawing roller and a drying box, the height of the air layer is 10mm, the coagulating bath is a mixed solution of citric acid, sodium citrate, ethylene glycol and water, the mass ratio is 14:5:80:110, the coagulating bath temperature is 25 ℃, the cleaning tank solution is water, the first drawing multiple is 1.2, the second drawing multiple is 1.0, and the drying temperature is 80 ℃.
In order to verify that the modified bamboo charcoal/regenerated cellulose composite fibers in examples 1 and 2 were successfully obtained, fig. 1 (a) shows a surface micro-morphology map of the bamboo charcoal fiber prepared in example 1 of the present invention, fig. 1 (b) shows a surface micro-morphology map of the bamboo charcoal fiber prepared in example 2 of the present invention, fig. 2 (a) and (b) show a transverse cross-section and a vertical cross-section micro-morphology map of the bamboo charcoal fiber prepared in example 1 of the present invention, respectively, and fig. 2 (c) and (d) show a transverse cross-section and a vertical cross-section micro-morphology map of the bamboo charcoal fiber prepared in example 2 of the present invention, respectively, the modified bamboo charcoal/regenerated cellulose composite fiber of the present invention has a large specific surface area and a large number of micropores and mesopores, and the prepared modified bamboo charcoal regenerated cellulose fiber has excellent adsorption performance.
Example 3
The embodiment is basically the same as the embodiment 1, except that the step S1 is to wash the bamboo wood at 80 ℃ and dry for 3 hours, and the step S3 is to wash the bamboo charcoal blank to be neutral and dry for 3 hours at 80 ℃ to obtain the bamboo charcoal with carbon nitrogen ratio of 98.34.
Example 4
The embodiment is basically the same as the embodiment 1, except that the step S2 is to treat the dried bamboo at 300 ℃ in nitrogen atmosphere for 2 hours, raise the temperature to 600 ℃ and treat for 3 hours to complete carbonization, gradually cool the carbonized bamboo charcoal from 600 ℃ to 60 ℃ to obtain bamboo charcoal blank, and finally obtain bamboo charcoal with carbon nitrogen ratio of 135.42.
Example 5
The embodiment is basically the same as the embodiment 1, except that the step S2 is to treat the dried bamboo at 230 ℃ for 1h in nitrogen atmosphere, raise the temperature to 450 ℃ and treat for 3h to complete carbonization, gradually cool the carbonized bamboo charcoal from 450 ℃ to 50 ℃ to obtain bamboo charcoal blank, and finally obtain the bamboo charcoal with carbon nitrogen ratio of 86.25.
Comparative example 1
The comparative example is basically the same as example 1, except that no bamboo charcoal is used, and the preparation method comprises the steps of adding 12.5g of crushed bamboo pulp into 220g of urea/tetrabutylammonium hydroxide mixed solvent (the mass ratio is 2:5, the tetrabutylammonium hydroxide solution is 40% aqueous solution), stirring and dissolving to obtain spinning solution, centrifuging the spinning solution to remove bubbles, carrying out wet spinning, and sequentially passing through a coagulating bath, a first drawing roller, a water bath, a second drawing roller and a drying box to obtain fibers, wherein the coagulating bath is a mixed solution of citric acid, sodium citrate, ethylene glycol and water, the mass ratio is 14:5:80:110, the coagulating bath temperature is 25 ℃, the cleaning tank solution is water, the first drawing multiple is 1.1, the second drawing multiple is 1.0, and the drying temperature is 80 ℃.
Comparative example 2
The comparative example is basically the same as example 1, except that the steps S5 and S6 are not included, 1.1g of bamboo charcoal particles are added into 220g of urea/tetrabutylammonium hydroxide mixed solvent (the mass ratio is 2:5, the tetrabutylammonium hydroxide solution is 40% aqueous solution), the solvent is uniformly dispersed by stirring, and 12.5g of crushed bamboo pulp is added into the mixed solvent to be stirred and dissolved, so that the bamboo charcoal regenerated cellulose fiber spinning solution is obtained.
Comparative example 3
The comparative example is substantially the same as example 1, except that S6 is a process of centrifugally washing the polydopamine modified bamboo charcoal dispersion at 4000r/min, washing with water to remove organic monomers, and vacuum drying at 60℃to obtain modified bamboo charcoal.
Comparative example 4
The comparative example is basically the same as example 1, except that in the step S5, 2g of bamboo charcoal is dispersed in 100ml of water, stirred for 5min, then ultrasonically oscillated for 10min, 1g of dopamine is added for magnetic stirring, 1.3g of tris buffer is added, the pH value of the mixed solution is adjusted to 8.5, and the mixture is stirred for 4h, thus obtaining polydopamine modified bamboo charcoal dispersion.
Comparative example 5
The comparative example is basically the same as example 1, except that there are no S1, S2 and S3 steps, and that in S4 step, the commercial bamboo charcoal with carbon nitrogen ratio of 23.63 is put into a high-energy ball mill for ball milling for 5 hours, the particle size is 2 μm after grinding, 10g of refined bamboo charcoal powder is mixed with 1000ml of water, and the washing cycle is carried out for 2 times at 4000r/min, and the washed bamboo charcoal is dried in a drying oven to obtain bamboo charcoal particles.
Comparative example 6
The comparative example is basically the same as example 1, except that there are no S1, S2 and S3 steps, and that in S4 step, commercially available bamboo charcoal with carbon nitrogen ratio of 158.93 is put into a high-energy ball mill for ball milling for 5 hours, the particle size is 2 μm after grinding, 10g of refined bamboo charcoal powder is mixed with 1000ml of water, centrifugal washing is carried out for 2 times at 4000r/min, and the washed bamboo charcoal is dried in a drying oven to obtain bamboo charcoal particles.
Comparative example 7
This comparative example is substantially the same as example 1 except that in step S5, the pH of the mixed solution is adjusted to 5.8.
Comparative example 8
This comparative example is substantially the same as example 1 except that the pH of the mixed solution is adjusted to 10 in step S5.
Performance test the fibers obtained in examples 1 to 5 and comparative examples 1 to 8 were subjected to performance tests of antibacterial property, elongation at break and breaking strength in this order.
Antibacterial property, namely placing 3mm round antibacterial test fiber on a bacterial culture dish, culturing for 12 hours, and observing and measuring the control efficacy.
Elongation at break and breaking strength were measured with reference to GB/T14337-2008 method for testing tensile Property of chemical fiber and staple fiber.
The results of the performance tests of the antibacterial properties, elongation at break and breaking strength of examples 1 to 5 and comparative examples 1 to 8 are shown in Table 1.
Table 1:
As can be seen from the test results of Table 1, compared with the comparative examples 1 and 2, the embodiment 1 of the invention can obviously improve the density of active groups on the surface of bamboo charcoal particles by adopting high-density modification of polydopamine on the surface of bamboo charcoal materials compared with the non-added bamboo charcoal and the non-modified bamboo charcoal, is beneficial to improving the grafting efficiency of polysiloxane quaternary ammonium salt after secondary modification, and simultaneously, increases the number of active sites on the surface of the bamboo charcoal by utilizing the modification effect and the firm combination of nano particles, so that the grafting efficiency of the bamboo charcoal and the polysiloxane quaternary ammonium salt is further improved, and the interaction of functional bamboo charcoal filler and a matrix and the dispersibility in the matrix are realized, so that the prepared modified bamboo charcoal/regenerated cellulose composite fiber has excellent antibacterial property and mechanical property.
As can be seen from comparison of the embodiment 1 and the embodiment 3, in the preparation of the bamboo charcoal, in the pretreatment of drying the bamboo and the post-treatment of cleaning and drying the bamboo charcoal blank, the influence on the carbon-nitrogen ratio of the prepared bamboo charcoal is small, mainly the removal of water and cleaning, the influence on the moisture content and cleanliness of the bamboo is small, the direct influence on the carbon-nitrogen ratio is small, and as the carbonization temperature is increased, the organic matters in the bamboo can undergo more severe pyrolysis and polycondensation reaction, the release of the non-carbon elements in the form of gas can be promoted, the carbon content in the bamboo charcoal is increased, the nitrogen content is reduced, the carbon-nitrogen ratio is further increased, and conversely, the lower carbonization temperature can slow down the speed of the pyrolysis and polycondensation reaction, so that more nitrogen elements remain in the bamboo charcoal, thereby reducing the carbon-nitrogen ratio, and simultaneously, the further release of the non-carbon elements is facilitated, and the shorter carbonization time is not enough to effectively release all the non-carbon elements, so that the nitrogen content in the bamboo charcoal is relatively high, and the carbonization time is effectively changed when the carbonization time is adjusted and controlled by the pretreatment of the bamboo charcoal.
As can be seen from the comparison between the embodiment 1 and the comparative examples 3 and 4, the high carbon-nitrogen ratio bamboo charcoal has more micropores, specific surface area and unsaturated bonds, is favorable for the deposition of polydopamine on the surface of the bamboo charcoal to be more uniform, increases the available space of surface active groups, has more carbon-based active sites on the surface of the high carbon-nitrogen ratio bamboo charcoal, can be used as the catalytic center of polydopamine polymerization reaction, enables carbon atoms in the bamboo charcoal to form stronger chemical bonds with nitrogen atoms in polydopamine, can enable interaction between the bamboo charcoal and polydopamine to be stronger, and further enhances the interfacial binding force between the bamboo charcoal and polydopamine, therefore, the method is favorable for improving the grafting effect, further improving the antibacterial property and mechanical property of the bamboo charcoal, and simultaneously, the bamboo charcoal with the excessively low carbon-nitrogen ratio or the excessively high carbon-nitrogen ratio has a certain influence on the subsequent modification and grafting effect, so that the antibacterial property and mechanical property of the bamboo charcoal are further influenced, because the surface active sites of the bamboo charcoal with the excessively low carbon-nitrogen ratio are fewer, and more defects or vacancies exist in a carbon skeleton, the bamboo charcoal is easily damaged in the modification and grafting processes, the performance is reduced, and the carbon skeleton structure of the bamboo charcoal is damaged due to the excessively high carbon-nitrogen ratio, and the adhesion and the distribution of modified and grafted molecules on the surface of the bamboo charcoal are influenced, so that the mechanical property is reduced, and the antibacterial property of the bamboo charcoal is influenced.
As can be seen from the comparison between the embodiment 1 and the comparative example 5, the hydrophilic and antibacterial properties of the bamboo charcoal are enhanced, the long-chain structure of the polysiloxane quaternary ammonium salt is also beneficial to improving the dispersibility of the bamboo charcoal in the regenerated cellulose matrix, and further, the mechanical properties of the fiber are also affected to a certain extent, because the polysiloxane quaternary ammonium salt molecule contains quaternary ammonium groups, the poly-dopamine layer formed by dopamine on the surface of the bamboo charcoal has good adhesiveness and reactivity, and further, when the polysiloxane quaternary ammonium salt is grafted to the surface of the bamboo charcoal through chemical bonds, the quaternary ammonium groups are firmly fixed on the bamboo charcoal particles, and the antibacterial properties of the fiber are effectively improved along with the dispersion of the bamboo charcoal particles in the regenerated cellulose fiber, and meanwhile, the functional groups in the polysiloxane quaternary ammonium salt molecule can form hydrogen bonds or ionic bonds with the groups such as hydroxyl groups in the surface of the bamboo charcoal and the regenerated cellulose fiber, so that the compatibility between the bamboo charcoal and the regenerated cellulose is enhanced, and the interfacial binding force between the bamboo charcoal and the regenerated cellulose is improved, and the mechanical properties of the fiber are better improved.
As can be seen from a comparison of the examples 1, 2 and 6, the functional nanoparticles endow the composite fiber with additional antibacterial and mechanical properties, because the positive charges on the surfaces of the functional nanoparticles and the negative charges on the cell walls of bacteria, the generated difference enables the nanoparticles to be strongly adsorbed on the surfaces of bacteria and damage the integrity of cell membranes of the bacteria through electrostatic interaction, meanwhile, the active sites on the surfaces of the nanoparticles can react with biomolecules in the bacteria to further inhibit or kill the bacteria, and the functional nanoparticles have larger specific surface area and rich surface chemical properties, so that the nanoparticles can form strong interaction with the active sites on the surfaces of the bamboo charcoal, the number of the active sites on the surfaces of the bamboo charcoal is increased, more grafting positions are provided for the polysiloxane quaternary ammonium salt, and therefore, the grafting efficiency is improved, and the antibacterial and mechanical properties are further improved.
As can be seen from the comparison between the example 1 and the comparative example 7, when the self-polymerization process of dopamine is inhibited in an acidic environment, the formation of polydopamine is blocked, the antibacterial agent on the surfaces of nanoparticles cannot be effectively fixed or distributed unevenly, and the functional nanoparticles are easy to dissolve and destroy in structure in the acidic environment, so that the overall antibacterial performance is reduced, and the mechanical properties are reduced, and in an alkaline environment, the functional groups such as amino groups and catechol groups in dopamine molecules are easier to deprotonate, negative ions are formed, electrostatic interactions and hydrogen bonding can occur, the self-polymerization capability of dopamine is promoted, the antibacterial agent can be applied to the surface modification of the functional nanoparticles, the stability and dispersibility of the surface of the nanoparticles in an aqueous solution can be remarkably improved, and agglomeration is prevented, so that the synergistic effect of dopamine, the functional nanoparticles and the quaternary ammonium salt of polysiloxane is realized, the antibacterial effect and the mechanical properties are effectively improved, and the stability of the antibacterial agent is reduced due to the fact that the self-polymerization of dopamine and the self-polymerization capability of the antibacterial agent are favorable in alkaline environment and the self-polymerization of dopamine and the antibacterial agent is reduced.
From the foregoing description it will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
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| CN101029420A (en) * | 2007-03-24 | 2007-09-05 | 山东海龙股份有限公司 | Bamboo charcoal viscose fiber and its manufacturing method |
| CN104532379A (en) * | 2014-12-22 | 2015-04-22 | 常熟市欧梦娜家纺有限公司 | Preparation method of nano-antibacterial bamboo carbon fiber |
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| CN101029420A (en) * | 2007-03-24 | 2007-09-05 | 山东海龙股份有限公司 | Bamboo charcoal viscose fiber and its manufacturing method |
| CN104532379A (en) * | 2014-12-22 | 2015-04-22 | 常熟市欧梦娜家纺有限公司 | Preparation method of nano-antibacterial bamboo carbon fiber |
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